JP2007186652A - Fine metal particle dispersion and method for producing the same, colored composition, photosensitive transfer material, shading image-having substrate, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fine metal particle dispersion having high dispersion stability, to provide a colored composition containing the fine metal particle dispersion, to provide a photosensitive transfer material using the colored composition, to provide a shading image-having substrate, to provide a color filter using the shading image-having substrate, and to provide a liquid crystal display device using the color filter. <P>SOLUTION: This method for producing the fine metal particle dispersion is characterized by having a process for washing and concentrating a dispersion containing fine metal particles and a sulfur-containing compound having a sulfur content of 3.0 mass% by ultrafiltration. The colored composition containing the fine metal particle dispersion. The photosensitive transfer material using the colored composition. The shading image-having substrate. The color filter using the shading image-having substrate. And the liquid crystal display device using the color filter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a metal fine particle dispersion and a production method thereof, a coloring composition, a photosensitive transfer material, a substrate with a light-shielding image, a color filter, and a liquid crystal display device.

Colored compositions using fine metal particles include printing inks, inkjet inks, etching resists, solder resists, plasma display panel (PDP) partition walls, dielectric patterns, electrode (conductor circuit) patterns, electronic component wiring patterns, and conductive pastes. Widely used for shading images such as conductive film and black matrix. Among the colored compositions, the colored composition for the black material is a black edge or red, blue, or the like provided in the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, or a CRT display device. In addition to a so-called black matrix (hereinafter also referred to as “BM”) such as a grid-like or stripe-like black portion between green pixels, and a dot-like or linear black pattern for light-shielding a TFT, various light-shielded images It is expected to be used for
BM is used to improve display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), is used to prevent deterioration in image quality due to current leakage due to light, and has high light shielding properties. (Optical density OD of 3 or more) is required.

  On the other hand, in recent years, liquid crystal display devices have been applied to TVs. However, since TVs have low transmittance and high luminance is obtained using high color purity color filters, the luminance of the backlight is high. The BM is required to have a high light-shielding property in order to prevent a decrease in contrast and see-through of the peripheral frame portion.

  Furthermore, since the TV is installed in a room where sunlight enters for a long time, there is a concern about deterioration of the TFT due to sunlight, and (1) a high OD gives a feeling of image tightening, that is, contrast. BM is required to have a high light-shielding property also in the sense that it is high and (2) the white color of the liquid crystal under external light becomes inconspicuous.

  As a method for forming a BM using a metal film such as chromium as a light shielding layer, for example, a metal thin film is prepared by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then a photo having a BM pattern is formed. There is a method of forming a BM by exposing and developing the photoresist layer using a mask, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film (see, for example, Non-Patent Document 1). .

  Since this method uses a metal thin film, there is an advantage that a high light shielding effect can be obtained even if the film thickness is small. However, there is a problem that a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required, which increases the cost and cannot be ignored. In addition, since it is a metal film, there is a problem that the reflectance is high and the display contrast is low under strong external light. On the other hand, as the metal thin film, there is a means of using a low-reflective chromium film (such as one made of two layers of metal chromium and chromium oxide), but it cannot be denied that the cost is further increased. And since the waste liquid containing a metal ion is discharged | emitted in an etching process, it also has the big fault that an environmental impact is large. In particular, chromium that is most frequently used is harmful and has a very large environmental impact. In recent years, as represented by the EU ELV and RoHS directives, there has been an increasing social interest in reducing environmental impact, and proposals have been made for materials that replace chromium.

As another BM forming method, a method using a light-sensitive pigment, for example, a photosensitive resin composition containing carbon black is also known. As the method, for example, after forming R, G, B pixels on a transparent substrate, a carbon black-containing photosensitive resin composition is applied onto the pixels, and the R, G, B pixel non-formation surface of the transparent substrate is applied. A self-aligned BM formation method in which the entire surface is exposed from the side is known (see, for example, Patent Document 1).
Although the manufacturing cost is lower than the method by etching the metal film, the method has a problem that the film thickness is increased in order to obtain sufficient light shielding properties. As a result, an overlap (step) between the BM and the R, G, and B pixels occurs, the flatness of the color filter deteriorates, and the cell gap unevenness of the liquid crystal display element occurs, leading to display defects such as display unevenness. Become.

Display unevenness is light unevenness observed when a gray test signal is input to the liquid crystal display device. It is said that when the surface of the black matrix substrate is not smooth, the orientation of the liquid crystal is disturbed, causing display unevenness. "Stripes" that appear to be relatively sharp and streaky are those that occur during the formation of alignment control protrusions such as thickness unevenness, exposure unevenness, development processing unevenness, heat treatment unevenness, etc. that occur during the formation of the photosensitive resin layer. In addition, when functioning as a liquid crystal display device, there may be unevenness caused by the interaction between the alignment control protrusion and the liquid crystal, but the mechanism is not clear.

On the other hand, a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate, and a relief is formed on the transparent substrate by exposure and development through a photomask having a pattern for BM. By contacting with an aqueous solution of a metal compound serving as a catalyst for plating, containing the metal compound in the relief, drying, applying heat treatment, and then bringing the relief on the transparent substrate into contact with an electroless plating solution, A method for producing a BM in which 0.01 to 0.05 μm of light shielding metal particles are uniformly dispersed therein has been proposed (for example, see Patent Document 2). Nickel, cobalt, iron, copper and chromium are described as the metal particles, and nickel is shown as a specific example.
However, this method has many troublesome processing steps for handling water, such as relief formation including exposure and development steps, application of an electroless plating catalyst, heat treatment, and electroless plating. Therefore, BM production at low cost cannot be expected greatly.

  In addition, in Patent Document 3 below, there is an example in which a magnetic filler is used as a coloring composition for producing a black pattern, but these examples are thick films of 10 microns or more, and the density per unit film thickness is low. It is not possible to produce a light-shielded image with high light-shielding performance at a low cost.

In addition to the above, a method using metal fine particles is known as a method for obtaining a black matrix with a small environmental load and a high optical density (see, for example, Patent Document 4 or 5). According to this method, it is said that a black matrix having a small optical load and a high optical density can be obtained.
However, when a light-shielding film was prepared using the coloring composition containing the above-mentioned metal fine particles and a high-definition matrix was formed by patterning exposure and development processing, the unevenness due to the aggregates of metal fine particles and liquid preparation were prepared at the time of light-shielding film preparation There is a problem that the coloring composition is not stable over time and cannot be stably produced, and technical improvement has been desired.

In order to improve the above technology, sufficient water washing is necessary from the viewpoint of removing impurities. A decantation method, an ultrafiltration method, a centrifugal separation method and the like are known as washing methods. Among these methods, the ultrafiltration method can be washed with water without reducing the distance between particles as compared with other methods, so that it can be washed with no aggregation. However, it is known that the solid content weight ratio increases when sufficient water washing is performed by ultrafiltration (see, for example, Patent Document 6). The particles having a large particle surface area and a high aspect ratio have a problem of aggregation due to the increase in the solid content weight ratio, and as a result, display unevenness occurs.
JP-A-62-9301 Japanese Patent No. 3318353 JP 2001-13678 A JP 2004-334180 A JP 2005-17322 A International Publication Number WO2002 / 094954 Published by Kyoritsu Shuppan Co., Ltd. “Color TFT LCD”, pp. 218-220 (April 10, 1997)

  The present invention has been made in view of the above problems, and a method for producing a metal fine particle dispersion with high dispersion stability, a metal fine particle dispersion obtained by the method, and a coating solution containing the metal fine particle dispersion over time. Stably produce light-shielded images such as black film or black matrix with high stability and low agglomerates, thin film with high black density (light shielding performance), or colored film with high density in thin film Coloring composition, photosensitive transfer material using the coloring composition, a substrate with a light-shielding image having excellent flatness, a color filter using the substrate with a light-shielding image, and low display unevenness using the color filter An object is to provide a liquid crystal display element.

That is, the present invention
<1> A method for producing a metal fine particle dispersion comprising a step of washing and concentrating a dispersion containing a sulfur-containing compound having a sulfur ratio of 3.0% by mass or more and metal fine particles by ultrafiltration. It is.

  <2> The method for producing a metal fine particle dispersion according to <1>, wherein the metal fine particles have an aspect ratio of 2 or more.

  <3> The method for producing a metal fine particle dispersion according to <1> or <2>, wherein the sulfur-containing compound has an acidic group.

  <4> The method for producing a fine metal particle dispersion according to <3>, wherein the acidic group is a carboxyl group.

  <5> The metal fine particles contain one or more metals selected from the group consisting of the fourth period, the fifth period, and the sixth period of the element periodic table. <1> to <4> The method for producing a metal fine particle dispersion according to any one of the above.

  <6> A metal fine particle dispersion produced by the method for producing a metal fine particle dispersion according to any one of <1> to <5>.

  <7> A colored composition containing at least the metal fine particle dispersion according to <6>.

  <8> A photosensitive transfer material comprising at least a photosensitive light-shielding layer on a support, wherein the photosensitive light-shielding layer contains the colored composition according to <7>. is there.

  <9> A substrate with a light-shielding image, characterized by having a light-shielding image formed using the colored composition according to <7>.

  <10> A substrate with a light-shielding image, characterized by having a light-shielded image formed using the photosensitive transfer material according to <8>.

  <11> A color filter produced using the substrate with a light-shielding image according to <9> or <10>.

  <12> A liquid crystal display device produced using the color filter according to <11>.

  According to the present invention, a method for producing a metal fine particle dispersion having a high dispersion stability, a metal fine particle dispersion obtained by the method, a coating liquid containing the metal fine particle dispersion, having a high stability with time and a small amount of aggregates, and a thin film And a colored composition capable of stably producing a light-shielded image including a black film or black matrix having a high black density (light-shielding performance), or a colored film having a high density in a thin film, and this colored composition There are provided a photosensitive transfer material using a material, a substrate with a light-shielding image having excellent flatness, a color filter using the substrate with a light-shielding image, and a liquid crystal display element having low display unevenness using the color filter.

Hereinafter, the metal fine particle dispersion and the production method thereof, the coloring composition, the photosensitive transfer material, the substrate with a light-shielding image, the color filter, and the liquid crystal display device of the present invention will be described in detail.
<Metal fine particle dispersion and production method thereof>
The method for producing a metal fine particle dispersion of the present invention comprises a sulfur-containing compound having a sulfur ratio of 3.0% by mass or more (hereinafter sometimes referred to as a sulfur-containing compound according to the present invention) and metal fine particles. It has the process of wash | cleaning and concentrating a liquid by ultrafiltration.
When ultrafiltration is performed when the dispersion contains a large amount of impurities, it is necessary to increase the number of times of washing with water, and conventionally, when the number of times of washing with water is large, metal fine particles in the dispersion may be aggregated. In the method for producing a metal fine particle dispersion of the present invention, ultrafiltration is performed in a state where a sulfur-containing compound having a sulfur ratio of 3.0% by mass or more is added to the dispersion. Aggregation can be prevented.

When the sulfur content of the sulfur-containing compound according to the present invention is less than 3.0% by mass, a decrease in dispersion stability or a decrease in stability over time, a decrease in quality, display unevenness, or the like may occur.
The preferable range of the sulfur content of the sulfur-containing compound according to the present invention is 4.5% by mass or more, and more preferably 6.0% by mass or more. If the sulfur content of the sulfur-containing compound according to the present invention is too large, the steric hindrance is weakened and the dispersion stability is lowered, possibly causing deterioration of stability over time, deterioration of quality, display unevenness, and the like. Therefore, the sulfur content of the sulfur-containing compound according to the present invention is preferably 30.0% by mass or less.

The sulfur-containing compound according to the present invention is not particularly limited as long as the sulfur content is 3.0% by mass or more, and examples thereof include compounds containing a thioether group, a mercapto group, a sulfide group, a thioxo group, and the like. However, it is preferable to have an acidic group in the molecule. Thereby, since high dispersion stability is maintained both at the time of particle formation and at the time of preparing the coating solution, a black matrix having high quality and no display unevenness can be produced.
The acidic group contained in the sulfur-containing compound according to the present invention is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boronic acid, a phenol, and a sulfoamide. The group is preferable because it has a particularly high dispersion stability during preparation of the coating solution and can produce a black matrix having high quality and no display unevenness.

  The sulfur-containing compound according to the present invention may be a polymer compound having at least one thioether group (hereinafter sometimes referred to as a polymer dispersant according to the present invention). By using a polymer compound having at least one thioether group, the dispersion stability of the metal fine particles can be improved. In the present invention, among such polymer compounds, compounds having a thioether group in the side chain portion of the polymer are preferred.

  Among these, a polymer compound having a repeating unit derived from an ethylenically unsaturated monomer containing at least one thioether structure in the side chain as the polymer structural unit is preferable, represented by the following general formula (1). A polymer compound having at least one type of repeating unit represented is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a sec butyl group, an isobutyl group, and a tert-butyl group. Groups are preferred.

In the general formula (1), R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms. The group, the aryl group, and the aralkyl group may each independently be unsubstituted or substituted, and may form a saturated or unsaturated cyclic structure.

The alkyl group having 1 to 18 carbon atoms represented by R ² may be unsubstituted or substituted, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, Examples thereof include alkyl groups such as sec-butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, dodecyl group and stearyl group. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.

  Among the above, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tert-butyl group. Is particularly preferred.

The aryl group having 6 to 14 carbon atoms represented by R ² may be unsubstituted or substituted, for example, an aryl such as a phenyl group, a toluyl group, a xylyl group, a naphthyl group, or an anthracenyl group. Groups. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

The aralkyl group having 7 to 16 carbon atoms represented by R ² may be unsubstituted or substituted, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthracenylmethyl group. An aralkyl group is mentioned. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aralkyl group having 7 to 11 carbon atoms is preferable, and a benzyl group is particularly preferable.

In the general formula (1), Z represents —O— or —NH—. Y represents a divalent linking group having 1 to 8 carbon atoms in total.
The divalent linking group having 1 to 8 carbon atoms represented by Y is, for example, an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, pentylene group), alkenylene group (eg, ethenylene group, Propenylene group), alkynylene group (eg, ethynylene group, propynylene group), arylene group (eg, phenylene group), divalent heterocyclic group (eg, 6-chloro-1,3,5-triazine-2, 4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl group), -O-, -CO-, -NR- (R is a hydrogen atom, Represents an alkyl group or an aryl group), or a combination thereof (for example, —NHCH ₂ CH ₂ NH—, —NHCONH—, etc.).

The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group represented by Y, and the alkyl group or aryl group represented by R may have a substituent. Examples of the substituent are the same as those of the aryl group represented by R ² . The alkyl group and aryl group represented by R are synonymous with the alkyl group and aryl group represented by R ² described above.

Of the divalent linking groups having 1 to 8 carbon atoms represented by Y, divalent linking groups having 1 to 6 carbon atoms are preferred, and among them, an ethylene group, a propylene group, a butylene group, a hexylene group,- CH ₂ —CH (OH) —CH ₂ — and —C ₂ H ₄ —O—C ₂ H ₄ — are particularly preferred.

The polymer dispersant according to the present invention may be a polymer compound containing two or more sulfur atoms by copolymerizing not only one type of repeating unit represented by the general formula (1) but also two or more types. Good. In addition, the thioether structure constituting the side chain is not only one sulfur atom but also a side chain having two or more sulfur atoms by constituting the Z and R ² with a group having a sulfur atom. Can do.

  The polymer dispersant according to the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain), or homopolymerization of a monomer having a thioether group (preferably in a side chain), or thioether It can be obtained by copolymerization of a monomer having a group (preferably in the side chain) with another monomer. Preferably, a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or homopolymerization of an ethylenically unsaturated monomer containing a thioether structure in the side chain, or an ethylenically unsaturated group containing a thioether structure in the side chain. It can be obtained by copolymerization of a saturated monomer and another copolymer component.

  Specific examples of the repeating unit represented by the general formula (1) are shown below. However, the present invention is not limited to these.

Among the above, in particular, R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, an ethyl group, a normal propyl group, a normal butyl group, a tert-butyl group, or a phenyl group, and Z is — A compound that is O- and Y is an ethylene group is preferred.

The polymer dispersant according to the present invention may be a copolymer of the repeating unit represented by the general formula (1) and another vinyl monomer.
Other vinyl monomers include aromatic vinyl compounds (eg, styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, etc.), vinyl cyanide (eg, (meth) acrylonitrile, and α- Chloroacrylonitrile, etc.), carboxylic acid vinyl esters (eg, vinyl acetate, vinyl benzoate, vinyl formate, etc.), aliphatic conjugated dienes (eg, 1,3-butadiene, isoprene, etc.), (meth) acrylic acid alkyl esters ( Examples, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate), (meth) acrylic acid alkylaryl esters ( Example, benzyl (meth) acrylate ), (Meth) acrylic acid substituted alkyl esters (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.)), alkyl (meta ) Acrylamide (eg, (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and tert-octyl (meth) acrylamide) Substituted alkyl (meth) acrylamides (eg, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, etc.), polymerizable oligomers (eg, one-end methacryloylated polymer) Methacrylate oligomer having a methacryloyl group at one end a polystyrene oligomer, and having a methacryloyl group at one end of polyethylene glycol, and the like) are preferably used.

  The polymerization ratio of the repeating unit represented by the general formula (1) in the polymer compound having at least one thioether group (the polymer dispersant according to the present invention) is preferably 1 to 100% in terms of mass fraction. -80% is more preferable, and 10-50% is particularly preferable. When the polymerization ratio is within the above range, the dispersion stability of the metal fine particles can be further improved.

  In addition, the polymer dispersant according to the present invention is preferably a polymer compound having an acidic group in the molecule from the viewpoint that alkali developability can be imparted if necessary. As the acidic group, for example, a group such as a carboxylic acid group, a sulfonic acid, a phosphoric acid, a boronic acid, a phenol, and a sulfoamide is preferable, and a polymer compound having at least one carboxylic acid group is particularly preferable.

  When alkali development is required, the polymer dispersant according to the present invention preferably has an acid value of 20 to 250 mgKOH / g, more preferably 50 to 200 mgKOH / g, and 70 to 180 mgKOH / g. Most preferably. When the acid value is within the above range, the dispersion stability is good and the alkali developability is also good.

  The molecular weight of the polymer dispersant according to the present invention is preferably 2,000 to 1,000,000, more preferably 3,000 to 200,000, and most preferably 5,000 to 100,000 in terms of weight average molecular weight. preferable. When the weight average molecular weight is within the above range, it is effective for improving dispersibility, good film strength can be obtained, and developability is not hindered.

  As content in the dispersion liquid of the sulfur containing compound which concerns on this invention, 1-40 mass% is preferable with respect to the mass of a metal microparticle, 3-30 mass% is more preferable, 5-20 mass% is further more preferable. . When the content is within the above range, the sulfur-containing compound according to the present invention is sufficiently adsorbed on the metal fine particles to improve dispersibility, and it is effective in improving hue and optical density by suppressing hue change due to heat. Therefore, it does not interfere with developability.

Particles having a metal solids aspect ratio of 2.0 or more have a large surface area and are difficult to maintain dispersion stability. The effect of the present invention is remarkably exerted on such a metal fine particle dispersion containing many metal fine particles having an aspect ratio of 2.0 or more.
In the present invention, the “aspect ratio” is an average value of the value (aspect ratio) obtained by dividing the longest diameter of the metal fine particles by the minimum diameter. About the tabular grain which has a grain diameter, it is the average value of the value (aspect ratio) which divided the grain diameter by thickness, respectively. The particle thickness can be easily measured by using a reference latex, measuring the shadow length on an electron micrograph, and referring to the latex shadow length. The aspect ratio according to the present invention is an average value of aspect ratios measured for 1000 metal fine particles.
The preferred aspect ratio of the metal fine particles used in the present invention is 2.0 or more, more preferably 2.5 or more, and particularly preferably 3.0 or more. Further, the aspect ratio of the metal fine particles is preferably 100 or less because the surface area increases as the aspect ratio increases and the dispersion stability decreases.
The shape of the metal fine particles used in the present invention is not particularly limited, but an oval shape, a plate shape (triangle, hexagonal shape, circular shape), or the like is preferable. Most preferred is a plate shape (triangle, hexagon, circle).

The composition of the metal fine particles used in the present invention is not particularly limited, and any composition may be used. As the metal fine particles in the present invention, one or more metals selected from the group consisting of, for example, the fourth period, the fifth period, and the sixth period of the periodic table of the long periodic table (IUPAC 1991) are used. It is preferable to contain, and one or more metals selected from the group consisting of Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14 It is preferable to contain 2 or more types.
Among these metals, the metal fine particles in the present invention are metals of the fourth period, the fifth period, or the sixth period, and are Group 2, Group 10, Group 11, Group 12, or Group 14. Group metals are more preferred, with calcium, gold, silver, copper, platinum, tin or palladium being particularly preferred. Among these, gold, silver, copper, and tin are preferable, and silver is particularly preferable. In the production of metal fine particles, two or more of the above metals may be used in combination, or may be used as an alloy.

In addition to commercially available metal fine particles, it can be prepared by a chemical reduction method using a metal compound, an electroless plating method, a metal evaporation method, a light irradiation method using a high-pressure mercury lamp, or the like. is there.
The metal compound is not particularly limited as long as it contains the above-mentioned metal. For example, tetrachloroauric (III) acid tetrahydrate (chloroauric acid), silver nitrate, silver acetate, silver perchlorate (IV) , Hexachloroplatinic acid (IV) hexahydrate (chloroplatinic acid), potassium chloroplatinate, copper (II) chloride dihydrate, copper (II) acetate monohydrate, copper (II) sulfate, palladium chloride (II) Dihydrate, rhodium trichloride (III) trihydrate, etc. can be mentioned. These can use 1 type (s) or 2 or more types.

  In the presence of the sulfur-containing compound according to the present invention, metal fine particles can be prepared by reducing the metal compound to a metal using a reducing compound.

  Examples of the reducing compound include amine compounds, alkali metal borohydrides such as sodium borohydride, hydrazine compounds, citric acid, tartaric acid, ascorbic acid, formic acid, formaldehyde, nitrous acid, sulfoxylate derivatives, hydroquinone, hydroquinone Derivatives, hydroxylacetone and the like. These can be used alone or in combination. As the reducing compound, triethanolamine, ascorbic acid, hydroquinone, hydroquinone derivatives, and hydroxylacetone are preferable, and ascorbic acid, hydroquinone, and hydroquinone derivatives are more preferable.

  It does not specifically limit as a method to add the said reducing compound, For example, it can carry out after addition of the sulfur containing compound which concerns on this invention. In this case, for example, the sulfur-containing compound according to the present invention is first dissolved in a solvent, and the reducing compound or the metal compound remains in a solution obtained by further dissolving either the reducing compound or the metal compound. By adding the method, the reduction can proceed. In addition, as a method of adding the reducing compound, first, the sulfur-containing compound according to the present invention is dissolved in a solvent, and further, the reducing compound and the metal compound are left at the same time or during addition. By adding, reduction can be advanced. As a method of adding the reducing compound, the sulfur-containing compound according to the present invention and the reducing compound or metal compound are mixed in advance, and this mixture is added to the remaining reducing compound or metal compound. It may take a form.

  The solvent used in the dispersion in the method for producing a metal fine particle dispersion of the present invention is not particularly limited as long as it can dissolve the metal compound, and examples thereof include water and organic solvents. . It does not specifically limit as said organic solvent etc., For example, C1-C4 alcohol, such as ethanol and ethylene glycol; Ketones, such as acetone; Esters, such as ethyl acetate, etc. are mentioned. As the solvent, one type or two or more types can be used. When the solvent is a mixture of water and an organic solvent, the organic solvent is preferably water-soluble, and examples thereof include acetone, methanol, ethanol, ethylene glycol, and the like. Water, alcohol and a mixed solution of water and alcohol are preferred.

  The sulfur-containing compound according to the present invention may be added in any process for producing a dispersion containing metal fine particles. You may add, when washing | cleaning and concentrating the dispersion liquid containing a metal microparticle by ultrafiltration.

By the reduction, a metal fine particle dispersion containing metal colloid particles having an average particle diameter of about 5 nm to 1000 nm is obtained. The metal fine particle dispersion after the reduction contains the metal colloid particles and the sulfur-containing compound according to the present invention, and becomes a colloid solution.
The average particle diameter is measured as follows using a photograph obtained by a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.). 100 particles are selected, the diameter of a circle having the same area as each particle image is defined as the particle diameter, and the average of the particle diameters of 100 particles is defined as the average particle size. A photograph taken at a magnification of 100,000 times and an acceleration voltage of 200 kV is used. The colloidal solution means a solution in which metal fine particles are dispersed in a solvent and are visible as a solution.

  Although it does not specifically limit as a filtration membrane used when wash | cleaning and concentrating a dispersion liquid by ultrafiltration, For example, resin-made things, such as polyacrylonitrile, a vinyl chloride / acrylonitrile copolymer, polysulfone, a polyimide, polyamide, are usually used. Things are used. Of these, polyacrylonitrile and polysulfone are preferable, and polysulfone is more preferable. The ultrafiltration filtration membrane is preferably a filtration membrane that can be back-washed from the viewpoint of efficiently washing the filtration membrane that is usually performed after the ultrafiltration.

  The metal fine particle dispersion of the present invention is produced by the above-described method for producing a metal fine particle dispersion of the present invention. The metal fine particle dispersion of the present invention contains at least the sulfur-containing compound and the metal fine particles according to the present invention.

<Coloring composition>
The colored composition of the present invention contains at least the metal fine particle dispersion of the present invention, and further contains at least one resin or precursor thereof, pigment fine particles, a polymer that serves as a binder, a monomer, an initiator, a solvent, and the like. You may contain.
The coloring composition of the present invention includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric pattern, and electrode (conductor circuit). It can be used for shading images such as patterns, wiring patterns of electronic components, conductive pastes, conductive films, black matrices, and the like. Preferably, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like for a display device, it can be suitably used for providing a light-shielded image on the spacing portion of the colored pattern, the peripheral portion, the outside light side of the TFT, and the like . Particularly preferably, a black edge provided at the periphery of a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, or a grid or stripe between red, blue, and green pixels. The black portion is more preferably used as a black matrix (BM) such as a dot-like or linear black pattern for shielding a TFT.

<Resin or its precursor>
Examples of the resin that may be contained in the colored composition of the present invention include polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, and JP-B-58-12777. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid as described in JP-A No. 54-25957, JP-A No. 59-53836, and JP-A No. 59-71048. Examples thereof include a copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and a cellulose derivative having a carboxylic acid group in the side chain. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 is also available. Can be mentioned.

It is preferable to select and use the resin having an acid value in the range of 30 to 400 mgKOH / g and a weight average molecular weight in the range of 1000 to 300,000. In addition to the above, in order to improve various performances, for example, the strength of the cured film, a sulfur-containing compound may be added within a range that does not adversely affect developability and the like. Examples of these alkali-soluble binder polymers include alcohol-soluble nylon and epoxy resin.
Examples of the resin precursor include a monomer that becomes a resin by curing. These will be described later.

<Pigment>
The fine metal particles in the colored composition of the present invention function as a pigment.
In addition to the metal fine particles, the colored composition of the present invention can contain pigment fine particles to make the hue close to black.
As a pigment to be contained in the coloring composition of the present invention, carbon black, titanium black, or graphite can be preferably used.
As an example of the carbon black, Pigment Black 7 (carbon black CI No. 77266) is preferable. Commercially available products include Mitsubishi Carbon Black MA100 (Mitsubishi Chemical Corporation) and Mitsubishi Carbon Black # 5 (Mitsubishi Chemical Corporation).

As an example of the titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. As commercial products, trade names: 12S and 13M manufactured by Mitsubishi Materials Corporation are listed. The particle size of titanium black used is preferably 40 to 100 nm.

  As an example of the graphite, those having a particle diameter of 3 μm or less as the Stokes diameter are preferable. Use of graphite exceeding 3 μm is not preferable because the contour shape of the light shielding pattern becomes non-uniform and sharpness deteriorates. Further, most of the particle diameter is desirably 0.1 μm or less.

  In addition to the pigment, a known pigment can also be used. In general, the pigment is roughly classified into an organic pigment and an inorganic pigment. In the present invention, the organic pigment is preferable. Examples of pigments that can be suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The hue of the organic pigment is preferably, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, or a black pigment. The pigments (coloring agents) used for the coloring composition are listed below, but are not limited thereto.

  Specific examples of the colorant used in the present invention include the coloring materials described in JP 2005-17716 A [0038] to [0040] and JP 2005-361447 A [0068] to [0072]. The pigment described in JP-A-2005-17521 and the colorants described in [0080] to [0088] can be suitably used.

  In addition to the above-mentioned colorants, refer to those described in “Handbook of Pigments, Japan Pigment Technical Association, Seibundo Shinkosha, 1989”, “COLOUR INDEX, THE SOCIETY OF DYES & COLORIST, THIRD EDITION, 1987”. Can be used as appropriate.

  It is desirable to use a pigment that has a complementary color relationship with the hue of the metal fine particles. Further, the pigments may be used alone or in combination of two or more. Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. And combinations of blue, violet and black pigments.

  The pigment is preferably uniformly dispersed in the composition. The average particle size of the pigment is preferably 5 nm to 5 μm, particularly preferably 10 nm to 1 μm, and more preferably 20 nm to 0.5 μm for color filters.

<Coloring composition for light-shielding image preparation>
The case where the colored composition is used as a colored composition for producing a light-shielding image (hereinafter also referred to as “light-shielding colored composition”) will be described in detail below.
When the light-shielding layer (the layer before patterning) is formed using the light-shielding coloring composition of the present invention, the optical density per 1 μm of the thickness of the light-shielding layer is preferably 1 or more. For example, in consideration of preventing metal fine particles from fusing during post-baking, such as during the production of a color filter, the content of metal fine particles in the light-shielding coloring composition is 10 in the light-shielding layer to be formed. It is preferable to adjust so that it may become about -90 mass%, Preferably it is about 10-80 mass%. The content is preferably determined in consideration of optical density variation due to the average particle size of the metal fine particles.
The same applies to the content of the metal fine particles in the coloring composition for shading having photosensitivity described below.

The “light-shielded image” referred to in the present invention is used to include a black matrix. “Black matrix” means a black edge provided around the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or a grid between red, blue and green pixels. And striped black parts, and dot-like and linear black patterns for TFT shading, etc. The definition of this black matrix is, for example, written by Taihei Kanno, “Liquid Crystal Display Equipment Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64. Examples of the light-shielded image include an organic EL display (for example, Japanese Patent Application Laid-Open No. 2004-103507), a front panel of a PDP (for example, Japanese Patent Application Laid-Open No. 2003-51261), and PALC for light shielding of a backlight.
The black matrix improves display contrast, and in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, it has high light shielding properties (optical density OD). 3 or more) is required.

<Coloring composition for photosensitive light-shielding image preparation>
More preferably, the colored composition for producing a light-shielding image has photosensitivity. Specifically, photosensitivity can be imparted by adding a photosensitive resin composition. The photosensitive resin composition has a polymer that serves as a binder, a photopolymerization initiator, and a monomer that has an ethylenically unsaturated double bond and undergoes addition polymerization upon irradiation with light (hereinafter sometimes referred to as “photopolymerizable monomer”). ) And the like are preferred.

The photosensitive resin composition includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those capable of developing with an aqueous alkali solution are preferred. For this purpose, the binder polymer is preferably an alkali-soluble polymer.
The photosensitive resin composition may be a negative type in which a portion that receives radiation such as light or electron beam as described above is cured, or a positive type in which a radiation non-receptive portion is cured.

  Examples of the positive photosensitive resin composition include those using a novolac resin. For example, an alkali-soluble novolak resin system described in JP-A-7-43899 can be used. Further, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication and a 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive agent and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be used. Furthermore, the composition described in JP-A-5-262850 can also be used.

Examples of the negative photosensitive resin composition include a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Is mentioned. Among them, particularly preferred is a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. As the photopolymerizable composition, “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” described in JP-A No. 11-133600, and other compositions can be used.
For example, as a photosensitive resin composition that can be developed in an aqueous alkali solution with a negative photosensitive resin composition, a carboxylic acid group-containing binder (alkali-soluble binder) as a main component, a photopolymerization initiator, a photopolymerizable monomer, The photosensitive resin composition which contains this is mentioned. As the alkali-soluble binder, the resins mentioned in the above <Resin or its precursor> can be preferably used.

  The alkali-soluble binder polymer is usually contained in an amount of 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive colored composition for producing a light-shielding image. In the range of 10 to 95% by mass, the adhesiveness of the photosensitive light-shielding layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.

Examples of the photopolymerization initiator include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512. Aromatic acyloin compounds substituted with α-hydrocarbons described in the specification, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, tria described in US Pat. No. 3,549,367 A combination of a reel imidazole dimer and a p-aminoketone, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, and a trihalomethyl-s described in US Pat. No. 4,239,850 -Triazine compounds, U.S. Pat. No. 4,221,976 Trihalomethyl oxadiazole compounds, and the like that are described in. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or in combination of two or more, and it is particularly preferable to use two or more. Moreover, 0.5-20 mass% is common and, as for content of the photoinitiator with respect to the total solid of the photosensitive resin composition, 1-15 mass% is preferable.

Examples of good display characteristics that are free from yellowing and can improve exposure sensitivity include a combination of a diazole photopolymerization initiator and a triazine photopolymerization initiator. Methyl 5- (p-styrylstyryl) -1,3,4-oxadiazole and 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) -3 ′ The combination of -bromophenyl] -s-triazine is the best.
The ratio of these photopolymerization initiators is a diazole / triazine mass ratio, preferably 95/5 to 20/80, more preferably 90/10 to 30/70, most preferably 80/20 to 60 /. 40. These photopolymerization initiators are described in JP-A-1-152449, JP-A-1-254918, and JP-A-2-153353.
Furthermore, a benzophenone series is also mentioned as a suitable example.

When the ratio of the pigment occupying the entire solid content of the photosensitive light-shielding image-forming colored composition is about 15 to 25% by mass, coloring such as yellowing can also be achieved by mixing a coumarin compound with the photopolymerization initiator. And high sensitivity can be achieved. As the coumarin compound, 7- [2- [4- (3-hydroxymethylbiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin is the best. The ratio of these photopolymerization initiator and coumarin compound is the mass ratio of photopolymerization initiator / coumarin compound, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, most preferably. Is 40/60 to 60/40.
However, the photopolymerizable composition that can be used in the present invention is not limited to these, and can be appropriately selected from known ones.

  The photopolymerization initiator is generally 0.5 to 20% by mass, preferably 1 to 15% by mass, based on the total solid content of the photosensitive colored composition for producing a light-shielding image. When the content is within the above range, a decrease in photosensitivity and image intensity can be prevented, and the performance can be sufficiently improved.

  Examples of the photopolymerizable monomer include compounds having a boiling point of 100 ° C. or higher at normal pressure. For example, monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tri Methylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Ethylene oxide and propylene oxide to polyfunctional alcohols such as dimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerol tri (meth) acrylate, trimethylolpropane or glycerol And polyfunctional (meth) acrylates such as those obtained by addition reaction of (meth) acrylate.

  Further, urethane acrylates disclosed in JP-B-48-41708, JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, are disclosed in each publication of No. 52-30490. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. The photopolymerizable monomers may be used alone or in combination of two or more. The content of the photopolymerizable monomer with respect to the total solid content of the photosensitive coloring composition for producing a light-shielding image is generally 5 to 50% by mass, and preferably 10 to 40% by mass. When the content is within the above range, the light sensitivity and the image strength are not lowered, and the adhesiveness of the photosensitive light-shielding layer is not excessive.

  As the photosensitive resin composition, it is preferable to add a thermal polymerization inhibitor in addition to the above components. Examples of the thermal polymerization inhibitor include aromatic hydroxy such as hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-butyl-p-cresol, β-naphthol, pyrogallol and the like. Compounds, quinones such as benzoquinone and p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine and phenothiazine, aluminum salt or ammonium salt of N-nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4,4′-thiobis ( 3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like.

  As the photosensitive resin composition, further known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, anti-sagging agents, leveling agents, antifoaming agents, flame retardants, Brighteners, solvents and the like can be added.

  Examples of the adhesion promoter include alkylphenol / formaldehyde novolak resin, polyvinyl ethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, Acrylic resin adhesives, aromatic, aliphatic or alicyclic petroleum resins, silane coupling agents and the like can be mentioned.

  Further, when the rod-shaped metal fine particles are used as an aqueous dispersion like silver colloid, it is necessary to use an aqueous one as the photosensitive resin composition. Examples of such a photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and commercially available products such as “SPP-” manufactured by Toyo Gosei Kogyo Co., Ltd. M20 "and the like.

  By forming the black matrix using the colored composition for producing a light-shielding image (including a photosensitive material) of the present invention, a black matrix having a thin film and a high optical density can be produced.

≪Photosensitive transfer material≫
In the present invention, a photosensitive transfer material for producing a light-shielding image is prepared using the above-described coloring composition for producing a light-shielding image, and a light-shielding image such as a black matrix is produced using the photosensitive transfer material. it can.
The photosensitive transfer material of the present invention is obtained by providing a photosensitive light-shielding layer formed on the support using the above-described photosensitive light-shielding image-forming colored composition containing at least the colored composition of the present invention. If necessary, a thermoplastic resin layer, an intermediate layer, or a protective layer can be provided.
The thickness of the photosensitive light-shielding layer is preferably in the range of 0.1 to 4 μm, particularly preferably in the range of 0.1 to 2.0 μm, and more preferably 0.2 to 1.0 μm.

<Support>
As the support in the photosensitive transfer material, a known support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the support is preferably about 15 to 200 μm, more preferably about 30 to 150 μm. When the thickness of the support is within the above range, it is possible to effectively suppress the occurrence of a wrinkle of a tin plate due to heat during the lamination process, which is advantageous in terms of cost.
Moreover, you may provide the electroconductive layer described in Unexamined-Japanese-Patent No. 11-149008 in the said support body as needed.

<Thermoplastic resin layer>
Moreover, it is preferable to provide an alkali-soluble thermoplastic resin layer between the support and the photosensitive light-shielding layer or between the support and the intermediate layer.
The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness on the base surface (including unevenness due to an image already formed, etc.). It preferably has a property that can be deformed.

  Examples of the resin contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth). Saponified product such as saponified product with acrylic ester copolymer, poly (meth) acrylic acid ester, and (meth) acrylic acid ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. It is preferable that there is at least one. In addition, use organic polymers soluble in alkaline aqueous solutions from the "Plastic Performance Handbook" (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). You can also. Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.

  Among the resins contained in the alkali-soluble thermoplastic resin layer, it is preferable to select and use a resin having a weight average molecular weight of 3,000 to 500,000 (Tg = 0 to 170 ° C.), and further a weight average molecular weight of 4 The range of 1,000 to 200,000 (Tg = 30 to 140 ° C.) is more preferable. Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-44615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP 60-159743, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-258539, JP JP 61-1669829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64- No. 5551, JP-A 64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-5-241340 Examples thereof include resins that are soluble in an alkaline aqueous solution.

  Of these, methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159, JP-B-55-38961, Examples thereof include styrene / (meth) acrylic acid copolymers described in each publication of No. 5-241340.

  The thermoplastic resin layer includes various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants, or release agents in order to adjust the adhesive force between the thermoplastic resin layer and the support. Etc. can be added. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate. The amount of the plasticizer in the thermoplastic resin layer is generally 200% by mass or less, preferably 20 to 100% by mass with respect to the thermoplastic resin.

  Further, the thickness of the alkali-soluble thermoplastic resin layer is preferably 6 μm or more. If the thickness of the thermoplastic resin is 6 μm or more, irregularities on the base surface can be completely absorbed. Further, the upper limit is generally about 100 μm or less, preferably about 50 μm or less, from the viewpoint of developability and production suitability.

  In the present invention, the solvent of the coating solution used when forming the thermoplastic resin layer can be used without particular limitation as long as it dissolves the resin constituting this layer. Examples of the solvent include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.

(Middle layer)
In the photosensitive transfer material of the present invention, an intermediate layer may be provided between the support and the photosensitive light-shielding layer.
The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble. Examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. . A resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as polyester, can also be used.
Of these, polyvinyl alcohol is preferred. The polyvinyl alcohol preferably has a saponification degree of 80% or more, more preferably 83 to 98%.

It is preferable to use a mixture of two or more resins constituting the intermediate layer, and it is particularly preferable to use a mixture of polyvinyl alcohol and polyvinyl pyrrolidone. The mass ratio between the two is preferably polyvinyl pyrrolidone / polyvinyl alcohol = 1/99 to 75/25, more preferably 10/90 to 50/50. When the mass ratio is within the above range, the surface shape of the intermediate layer is good, the adhesiveness with the photosensitive light-shielding layer coated thereon is good, and further, the oxygen barrier property is lowered and the sensitivity is lowered. Can be prevented.
In addition, an additive such as a surfactant can be added to the intermediate layer as necessary.

The thickness of the intermediate layer is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, it is possible to prevent an increase in the intermediate layer removal time during development without decreasing the oxygen barrier property.
The coating solvent for the intermediate layer is not particularly limited as long as the resin is dissolved, but water is particularly preferable, and a mixed solvent obtained by mixing the water-soluble organic solvent with water is also preferable. Specific examples of preferable coating solvents include, for example, water, water / methanol = 90/10, water / methanol = 70/30, water / methanol = 55/45, water / ethanol = 70/30, water / 1-propanol. = 70/30, water / acetone = 90/10, water / methyl ethyl ketone = 95/5 (where the ratio represents a mass ratio) and the like.

<Production of photosensitive transfer material>
In order to produce the photosensitive transfer material of the present invention, the support is prepared by applying, for example, a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, It can form by apply | coating and drying using coating machines, such as a wire bar coater and an extruder. When an alkali-soluble thermoplastic resin layer and an intermediate layer are provided, they can be formed in the same manner.

  Since the photosensitive transfer material of the present invention is provided with the photosensitive light-shielding layer using the colored composition for light-shielding image preparation of the present invention as described above, a light-shielding layer having a thin film and a high optical density can be produced. .

≪Method for producing shading image≫
In the present invention, the light-shielding image is produced by patterning a light-shielding layer formed using the colored composition or the photosensitive transfer material, and the film thickness of the light-shielding layer is about 0.2 to 2.0 μm, It is preferably 0.9 μm or less. Since the light shielding layer in the present invention is a dispersion of metal fine particles, even a thin film as described above can exhibit a sufficient optical density (3.5 or more).

  In addition, the method for producing (patterning) the light-shielded image using the colored composition for producing a light-shielded image of the present invention is not particularly limited. An example of a black matrix pattern forming method is given below.

  In the first method, a photosensitive composition containing metal fine particles is first coated with a coloring composition for producing a light-shielding image of the present invention containing metal fine particles and at least one of a resin or a precursor thereof and having photosensitivity. Forming a light shielding layer. Thereafter, a light shielding image is obtained by forming a pattern by removing the light shielding layer in portions other than the pattern by exposure and development. Further, a protective layer can be formed by forming a layer having the same composition as the above-described intermediate layer on the photosensitive light-shielding layer. In this case, the coating solution can be applied by using the coating machine described in <Preparation of photosensitive transfer material>, but it is preferable to perform the coating by a spin coating method.

  In the second method, first, metal fine particles and at least one kind of resin or its precursor are contained, and the non-photosensitive coloring composition for producing a light-shielding image of the present invention is applied to a substrate to contain rod-shaped metal fine particles. A light shielding layer is formed. Thereafter, a photosensitive resist solution is applied on the light shielding layer to form a resist layer. Next, the resist layer is exposed and developed by exposure to form a pattern in the resist layer, and then the non-patterned portion of the light shielding layer is dissolved according to this pattern to form a pattern in the light shielding layer. Finally, the resist layer is removed to produce a light-shielded image.

  In the third method, a coating layer is previously formed on a portion other than the pattern on the substrate, and contains metal fine particles and at least one of a resin or a precursor thereof, and is non-photosensitive in the present invention. A light-shielding layer containing a fine particle-containing layer is formed by applying a coloring composition for producing a light-shielding image. Next, the coating layer formed first is removed together with the upper light-shielding layer to produce a light-shielded image.

As a method for producing a light-shielded image using the photosensitive transfer material, the photosensitive transfer material is arranged and laminated on a light-transmitting substrate so that the photosensitive light-shielding layer of the photosensitive transfer material is in contact therewith. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light transmissive substrate, and then the layer is exposed and developed to form a light-shielded image.
This method for producing a light-shielded image does not require a cumbersome process and is low in cost.

Next, the exposure and development process will be described.
(Exposure and development)
A predetermined mask is disposed above the light-shielding layer formed on the substrate, then exposed from above the mask, then developed with a developer to obtain a patterning image, and subsequently subjected to a water washing treatment as necessary. The light-shielded image of the present invention can be obtained by the process of. In addition to the method of arranging the mask as described above, the pattern image may be obtained by performing relative scanning of the exposure light directly based on the image data without using the mask.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive light-shielding layer (eg, 365 nm, 405 nm, etc.). Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LD, an ultrahigh pressure mercury lamp, a YAG-SHG solid laser, a KrF laser, and a solid laser. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.
The exposure machine used at this time is not particularly limited, but in addition to the proximity exposure machine that exposes through the mask, a scattered light exposure machine, a parallel light exposure machine, a stepper, a laser exposure, etc. Can be used.

The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. Among them, a dilute aqueous solution of an alkaline substance is preferably used. Specifically, the developer is preferably one in which the photosensitive light-shielding layer exhibits a dissolution type development behavior. Further, a small amount of an organic solvent miscible with water may be added.
Further, before the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive light-shielding layer.

  Examples of the alkaline substance used in the development step include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, , Sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, Examples include monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “organic solvent miscible with water” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n- Preferable examples include butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. It is done. The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the light shielding layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time depends on the composition of the light-shielding layer, the alkalinity and temperature of the developing solution, and the type and concentration when an organic solvent is added, but is usually about 10 seconds to 2 minutes. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the light-shielded image shape suitable. In this development step, a light-shielded image is formed.

≪Substrate with shading image≫
The substrate with a light-shielding image of the present invention is produced by patterning a light-shielding layer formed using a coloring composition for producing a light-shielding image or a photosensitive transfer material on a light-transmitting substrate as described above.
The film thickness of the light-shielded image on this light-shielded image-attached substrate (preferably a black matrix substrate) is preferably 0.2 to 2.0 μm, particularly preferably 0.2 to 0.9 μm. Since the light shielding layer in the black matrix substrate is a dispersion of metal fine particles, even a thin film has a sufficient optical density.

  The board | substrate with a light-shielding image of this invention can be applied without a restriction | limiting in particular to uses, such as portable terminals, such as a television, a personal computer, a liquid crystal projector, a game machine, a mobile phone, a digital camera, and a car navigation system. Moreover, it can be used suitably also in preparation of the following color filter.

≪Color filter≫
The color filter of the present invention comprises two or more pixel groups that are formed of a colored layer and have different colors on a light-transmitting substrate, and each of the pixels constituting the pixel group is mutually shielded (hereinafter referred to as “black”). The black matrix is produced using the colored composition for producing a light-shielding image or the photosensitive transfer material of the present invention. The number of pixel groups may be two, three, or four or more. For example, in the case of three, three hues of red (R), green (G), and blue (B) are preferably used. When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable, and any arrangement may be used when four or more types of pixel groups are arranged.

As the light transmissive substrate, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
To produce a color filter, after forming two or more pixel groups on a light-transmitting substrate by a conventional method, a black matrix may be formed as described above, or a black matrix is first formed. Thereafter, two or more pixel groups may be formed.
Since the color filter of the present invention is provided with a black matrix having a high density and a thin film as described above, it has high display contrast and excellent flatness.

≪Display device≫
The color filter of the present invention can be suitably used for a display device. Examples of the display device include a plasma display device, an EL display device, a CRT display device, a liquid crystal display element, etc. Especially, when used for a liquid crystal display element, the effect of the colored composition for producing a light-shielding image of the present invention is remarkably exhibited. Is done. For definitions of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Sumo Industry Research Group 1990)”, “Display Device (written by Junyuki Ibuki, published in 1989 by Sangyo Tosho)” It is described in.

  The display device of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, in addition to the color filter. Generally composed of various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. The light-shielded image in the present invention can be applied to a liquid crystal display element composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Omoyoshi) The type of LCD includes STN, TN, VA, IPS, OCS, R-OCB, and the like.

As one of the liquid crystal display elements, at least one is provided with a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of light-transmitting substrates. Can be mentioned.
As the color filter, a color filter having a plurality of pixel groups as described above and each pixel constituting the pixel group being separated from each other by a light-shielded image according to the present invention can be suitably used. Since the color filter has high flatness, the liquid crystal display element including the color filter does not cause cell gap unevenness between the color filter and the substrate, and the occurrence of display defects such as color unevenness is improved.

In another aspect of the liquid crystal display element, at least one of them is provided with a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is an active element ( For example, a black matrix produced using the colored composition for producing a light-shielding image or the photosensitive transfer material of the present invention is formed between each active element.
The liquid crystal display element is described in, for example, “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Side Industry Research Committee, 1994)”. The display device (liquid crystal display element) of the present invention is not particularly limited, and can be applied to various types of liquid crystal display elements described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for color TFT type liquid crystal display elements.
The color TFT liquid crystal display element is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention can be applied to a liquid crystal display element with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  Examples of the liquid crystal that can be used for the liquid crystal display element include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited by the following Example.
[Example 1]
<Preparation of silver fine particle dispersion>
3 g of the following polymer compound D-1 containing 7.2% by mass of a sulfur atom was added to 2.5 L of an aqueous solution adjusted to pH 11.0 using a 1N aqueous sodium hydroxide solution, and dissolved until completely dissolved. Stir at 30 ° C. for 30 minutes.
The temperature of this solution was controlled at 45 ° C., and an aqueous solution containing 12 g of ascorbic acid and an aqueous solution containing 30 g of silver nitrate were added simultaneously to prepare a black silver fine particle dispersion. The obtained silver fine particles were amorphous potato-like particles having an arithmetic average particle diameter of 52 nm and an arithmetic standard deviation of 33 nm and having an aspect ratio of 1.0 to 5.0 (average aspect ratio of 3.5). The results are shown in Table 1.
Next, an ultrafiltration module SIP1013 (manufactured by Asahi Kasei Co., Ltd .; molecular weight cut off 6000), a magnet pump, and a stainless steel cup were connected with a silicon tube to obtain an ultrafiltration device. The silver fine particle dispersion (aqueous solution) was put into a stainless steel cup, and ultrafiltration was performed by operating a pump. When the filtrate from the module reached 2.5 liters, 2.5 liters of distilled water was added to the stainless steel cup for washing. After the above washing was repeated 10 times, concentration was performed until the amount of the mother liquor was 50 ml. This silver particle dispersion is designated as A-1 dispersion. 0.25 μml of this metal fine particle dispersion A-1 was placed in a 25 ml volumetric flask and diluted with distilled water. Using a “U-3410 self-recording spectrophotometer” manufactured by Hitachi, the concentration of the solution at 435 nm was measured. The sample was left in a room at a constant temperature of 25 ° C. for 2 weeks, and absorption was measured in the same manner. The absolute value of the change in concentration between the solution before aging and after 2 weeks was defined as “ΔW”, and stability over time was judged according to the following criteria. The results are shown in Table 2.
○: The absolute value of ΔW was less than 0.8.
X: The absolute value of ΔW was 0.8 or more.

<Preparation of coating solution for photosensitive light shielding layer>
The following composition was mixed and the coating liquid for photosensitive light shielding layers was prepared.
〔composition〕
・ A-1 dispersion 50.00g
・ Normal propanol 40.00g
・ Fluorosurfactant 0.5g
(F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Dipentaerythritol hexaacrylate 1.75g
(KAYARAD DPHA (Nippon Kayaku Co., Ltd.))
-Bis [4- [N- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.17 g
・ Acetone 415g

<Preparation of coating solution for protective layer>
The following compositions were mixed to prepare a protective layer coating solution.
・ Polyvinyl alcohol 3.0g
(Product name: PVA205, manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone 1.3g
(Product name: PVP-K30, manufactured by IPS Japan)
・ Distilled water 50.7g
・ Methyl alcohol 45.0g

<Production of photosensitive material>
On the glass substrate, the said light shielding layer coating liquid was apply | coated so that the dry film thickness might be set to 0.8 micrometer using a spin coater, and it dried at 100 degreeC for 5 minute (s), and formed the photosensitive light shielding layer. Next, the protective layer coating solution was applied onto the film so as to have a dry film thickness of 1.5 μm using a spin coater, and dried at 100 ° C. for 5 minutes to form a protective layer.

  Further, the photosensitive material prepared above was coated in the same manner as the photosensitive material Z-1 using the photosensitive light-shielding layer coloring composition that had been kept for two days from the time of preparation.

<Production of black matrix>
With a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and protective layer are The distance between the coated surfaces was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² . Next, development processing (33 ° C.) was performed using a development processing solution TCD (manufactured by Fuji Photo Film Co., Ltd., alkaline developer). A black matrix having a screen size of 10 inches, a number of pixels of 480 × 640, a black matrix width of 24 μm, and an opening of the pixel portion of 86 μm × 304 μm was obtained. The development time was defined as the shortest development time and the shortest development time × 1.2, which was the time until the glass surface was developed after the photocured film was developed with the above exposure amount.

<< Evaluation 1: Evaluation of pattern shape >>
The obtained black matrix was evaluated as follows. The results are shown in Table 2 below.
-Black matrix quality-
The pattern shape of the glass substrate on which the black matrix was formed was observed visually or with a microscope, and the line was straight and the presence or absence of disconnection was evaluated. A straight line where no disconnection was confirmed was marked with ◯, a non-straight line, and a broken line confirmed with x.

(Creation of liquid crystal display device)
A liquid crystal display device was produced by using the substrate formed with the black matrix obtained above and using the method described in the first example [0079] to [0082] of JP-A-11-242243. It was confirmed that it displayed without malfunction.

<< Evaluation 2 >>
The following evaluation was performed about the obtained liquid crystal display device. The results are shown in Table 2 below.
-Measurement of unevenness-
When a gray test signal was input to the liquid crystal display device, it was observed visually and with a magnifying glass to determine whether or not unevenness had occurred. The case where no unevenness was observed was marked with ◯, and the case where unevenness was confirmed was marked with ×.

[Example 2]
<Preparation of gold fine particle dispersion>
3 g of D-1 was added to 2.5 L of an aqueous solution adjusted to pH 11.0 using a 1N aqueous sodium hydroxide solution, and stirred at 45 ° C. for 30 minutes until it was completely dissolved.
The temperature of this solution was controlled at 75 ° C., and 600 cc of an aqueous solution containing 12 g of ascorbic acid and 1000 cc of an aqueous solution containing 74.8 g of tetrachloro (III) gold acid tetrahydrate were simultaneously added to prepare a gold fine particle dispersion. . This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Next, a gold fine particle dispersion (aqueous solution) was used in place of the silver fine particle dispersion of Example 1, and washing and concentration by ultrafiltration were performed in the same manner as in Example 1. Using the above gold fine particle dispersion instead of the silver fine particles of Example 1, a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2 below.

[Example 3]
<Preparation of AuAg alloy particle dispersion>
A solution was prepared by mixing 2782 g of distilled water and 150 g of a 1N aqueous sodium hydroxide solution. To this solution, 3 g of D-1 was added and stirred until completely dissolved. This solution is designated as solution G. 11.9 g of ascorbic acid was added to a solution obtained by mixing 231 g of a 1N sodium hydroxide aqueous solution with 208 g of distilled water, and stirred for 30 minutes until it was completely dissolved. Let this solution be H liquid. A solution was prepared by mixing 189 g of distilled water with 37.4 g of tetrachloro (III) gold acid tetrahydrate and 15.7 g of silver nitrate, and stirred for 30 minutes. This solution is designated as solution I. Here, the H liquid and the I liquid were simultaneously added to the G liquid which was temperature-controlled at 50 ° C. and stirred at 600 rpm with a Suriwan motor to prepare an AuAg alloy fine particle dispersion. This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Next, the AuAg alloy fine particle dispersion was used in place of the silver fine particles of Example 1, and washing and concentration by ultrafiltration were performed in the same manner as in Example 1. Using the AuAg alloy fine particle dispersion instead of the silver fine particles of Example 1, a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

[Example 4]
<Preparation of AgSn alloy particle dispersion>
31 g of silver (I) acetate, 87.3 g of tin (II) acetate, 70.2 g of gluconic acid, 60.3 g of sodium pyrophosphate and 3.0 g of D-1 were dissolved in 3082.6 ml of pure water to obtain a solution J. It was. Separately, 48.4 g of hydroxyacetone was dissolved in 451.6 ml of pure water to obtain a solution K. While the solution J obtained above was stirred at 1100 rpm while being kept at 25 ° C., the above solution K was added thereto over 2 minutes, and stirring was continued at 300 rpm for 6 hours. Then, the liquid mixture turned black, and silver tin (AgSn) alloy fine particles were obtained. This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Next, an AgSn fine particle dispersion (aqueous solution) was used in place of the silver fine particle dispersion of Example 1, and washing and concentration by ultrafiltration were performed in the same manner as in Example 1. Using the above AgSn alloy fine particle dispersion instead of the silver fine particles of Example 1, a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 1]
The silver nanopigment dispersion prepared in Example 1 was prepared in the same manner except that D-2 was used instead of D-1. This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Next, the above-mentioned silver fine particle dispersion was used in place of the silver fine particles of Example 1, and a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 2]
The gold fine particle dispersion prepared in Example 2 was prepared in the same manner except that D-2 was used instead of D-1. The results are shown in Tables 1 and 2. Next, the above-described gold fine particle dispersion was used in place of the gold fine particles of Example 1, and a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2 below.

[Comparative Example 3]
The AuAg fine particle dispersion prepared in Example 3 was prepared in the same manner except that D-2 was used instead of D-1. This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Next, in place of the gold-silver fine particles of Example 3, the above-described gold-silver fine particle dispersion was used, and a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 4]
The silver tin fine particle dispersion prepared in Example 4 was prepared in the same manner except that D-2 was used instead of D-1. This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. Next, in place of the silver tin fine particles of Example 4, the above-mentioned silver tin fine particle dispersion was used, and a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 5]
A silver fine particle dispersion was prepared in the same manner except that the silver fine particle dispersion prepared in Example 1 was subjected to centrifugal separation treatment (12000 rpm, 30 min) instead of the ultrafiltration step. This dispersion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Next, in place of the silver fine particles of Example 1, the above-mentioned silver-gold fine particle dispersion was used, and a black matrix and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

  From Table 2, the liquid crystal display device using the metal fine particle dispersion of the present invention has no display unevenness and good display quality.

Claims (12)

  A method for producing a metal fine particle dispersion, comprising a step of washing and concentrating a dispersion liquid containing a sulfur-containing compound having a sulfur ratio of 3.0% by mass or more and metal fine particles by ultrafiltration.   The method for producing a metal fine particle dispersion according to claim 1, wherein an aspect ratio of the metal fine particles is 2 or more.   The method for producing a metal fine particle dispersion according to claim 1 or 2, wherein the sulfur-containing compound has an acidic group.   The method for producing a metal fine particle dispersion according to claim 3, wherein the acidic group is a carboxyl group.   The metal fine particles contain one or more metals selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table of elements. A process for producing a metal fine particle dispersion as described in 1.   A metal fine particle dispersion produced by the method for producing a metal fine particle dispersion according to any one of claims 1 to 5.   A coloring composition comprising at least the metal fine particle dispersion according to claim 6. A photosensitive transfer material having at least a photosensitive light-shielding layer provided on a support,
The photosensitive transfer material, wherein the photosensitive light-shielding layer contains the colored composition according to claim 7.   A substrate with a light-shielding image, comprising a light-shielding image formed using the colored composition according to claim 7.   A substrate with a light-shielding image, comprising a light-shielding image formed using the photosensitive transfer material according to claim 8.   A color filter produced using the substrate with a light-shielding image according to claim 9.   A liquid crystal display device produced using the color filter according to claim 11.